JP2009242595A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in weather resistance and pigment coloring property, dissolving a bronze phenomenon and having a good balance between a surface appearance and impact resistance. <P>SOLUTION: The thermoplastic resin composition is composed of a graft copolymer (A) of 10-100 pts.wt. and a thermoplastic resin (B) of 0-90 pts.wt. (where the sum of (A) and (B) is 100 pts.wt.), wherein the graft copolymer (A) comprises a graft polymer (a-1) of 1-40 wt.%, which is formed by graft-polymerizing an aromatic vinyl compound and vinyl cyanide with a two layer structured rubber polymer of which the inner layer is a butadiene-based rubber polymer with a weight average particle size of 250-450 nm, and the outer layer is an acrylic rubber polymer with an average thickness of 70-180 nm, and a graft polymer (a-2) of 60-99 wt.%, which is formed by graft-polymerizing an aromatic vinyl monomer and vinyl cyanide monomer with an acrylic rubber polymer with a weight average particle size of 70-180 nm, and the thermoplastic resin (B) is formed by polymerizing one or more monomers of aromatic vinyl compound, vinyl cyanide, and a (meth)acrylic acid ester. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition that solves the bronze phenomenon and is excellent in impact resistance, weather resistance, and pigment colorability. More specifically, it has a good balance between surface appearance and impact resistance, and can be suitably used in a wide range of fields such as interior and exterior parts for vehicles such as automobiles, housings for various home appliances and OA equipment, and other miscellaneous goods fields. The present invention relates to a resin composition.

ABS resin is a resin with an excellent balance between impact resistance and workability, and is used in a wide range of fields such as interior and exterior parts for vehicles such as automobiles, housings for various home appliances and OA equipment, and other miscellaneous goods fields. .
However, the ABS resin has a disadvantage that the weather resistance is inferior because the butadiene rubber polymer used as the rubber component is easily decomposed by ultraviolet rays or the like.
Therefore, an AAS resin, in which the weather resistance is improved by replacing the rubber component in the ABS resin with an acrylic rubber polymer, has been put into practical use.
Usually, such a rubber-reinforced thermoplastic resin is colored by blending a colorant and is used as a colored molded product. One of the matters to be noted in this toning / coloring process is “metamerism”. This is a phenomenon in which the color changes when the light source changes. For example, it is often seen that the color under room light does not match the color under sunlight. This phenomenon is caused by the colorant and can be solved by selecting the colorant. This phenomenon can be easily determined with the naked eye, and can be confirmed by a spectrophotometer as a numerical value (reflectance) or a graph (reflectance curve).
However, colored molded articles have problems such as “bronze phenomenon” as well as the above-mentioned metamerism.
“Bronze phenomenon” is a red to yellow color other than the original colored hue under direct sunlight or transparent glass through direct sunlight even though the hue is good under indoor sunlight and indoor lighting. This is a phenomenon in which the colors in the range appear to overlap, and the quality image is deteriorated and the commercial value is lowered in the appearance of the molded product. Of course, this bronze phenomenon and metamerism are different phenomena. As a weather-resistant resin that solves such a bronze phenomenon, for example, a method is proposed in which the total amount of rubber particles having a weight average particle diameter in the range of 0.20 to 0.35 μm is less than 20% by weight based on the total weight of rubber. (Patent Document 1: Japanese Patent Laid-Open No. 63-275617). In addition, in Japanese Patent Application Laid-Open No. 2000-17135 (Patent Document 2), an AAS resin in which the bronzing phenomenon is solved by a method in which an acrylic ester rubber polymer having a weight average particle diameter of less than 0.2 μm is made 20% by weight or more Although a composition has been proposed, the impact resistance is not always satisfactory.
In JP 2007-77274 A (Patent Document 3), a weight average particle size of 0.30 to 0.45 μ acrylate rubber polymer and a weight average particle size of 0.15 to 0.30 μ acrylate. Although an AAS resin composition has been proposed in which the bronze phenomenon is solved and the impact resistance is improved by using a rubber-based polymer in combination, there has been a problem that pigment colorability is newly inferior.
JP-A 63-275617 JP 2000-17135 A JP 2007-77274 A

  The present invention provides a thermoplastic resin composition that solves the bronze phenomenon and is excellent in weather resistance and pigment colorability, and further has a good balance between surface appearance and impact resistance. It is the purpose.

The present inventors, as rubber components, a butadiene-based rubber polymer having a specific weight average particle diameter in the inner layer, a two-layer structure rubber polymer that is an acrylic rubber polymer having a specific thickness in the outer layer, and a specific weight By using an acrylic rubber polymer with an average particle diameter in combination, the bronze phenomenon was solved, the weather resistance, the surface appearance and the impact resistance were well balanced, and the pigment colorability was excellent, and the present invention was achieved. Is.
That is, the present invention
[1] A two-layer structure rubber polymer in which the inner layer is a butadiene rubber polymer having a weight average particle diameter of 250 nm to 400 nm and the outer layer has an average rubber thickness of 70 nm to 180 nm. 1 to 40% by weight of a graft polymer (a-1) obtained by graft polymerization of a monomer mainly composed of an aromatic vinyl monomer and a vinyl cyanide monomer,
A graft polymer obtained by graft polymerization of an acrylic rubber polymer having a weight average particle diameter of 70 nm to 180 nm with an aromatic vinyl monomer and a monomer mainly composed of vinyl cyanide monomer (a- 2) 10 to 100 parts by weight of the graft copolymer (A) comprising 60 to 99% by weight, an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth) acrylate monomer and other vinyls It consists of 0 to 90 parts by weight of a thermoplastic resin (B) obtained by polymerizing at least one monomer selected from the group consisting of monomers (however, the sum of (A) and (B) is 100 parts by weight). Thermoplastic resin composition,
[2] A butadiene-based rubber polymer in which a butadiene-based rubber polymer is agglomerated and enlarged to a weight-average particle size of 250 nm to 400 nm in a small particle size butadiene rubber polymer latex having a weight average particle size of 50 nm to 200 nm. The thermoplastic resin composition according to [1], which uses latex,
[3] A butadiene-based rubber polymer has a weight-average particle diameter of 50 nm to 200 nm and a small particle diameter butadiene-based rubber polymer latex is added with an acidic substance, and the latex has a pH lower than 7. The heat described in [1], wherein a butadiene-based rubber polymer latex is used which is stabilized by increasing the pH of the latex to be higher than 7 by adding a basic substance after the coagulation and enlargement to a diameter of 250 nm to 400 nm. A plastic resin composition is provided.

  The present invention provides a thermoplastic resin composition that solves the bronze phenomenon and is excellent in weather resistance and pigment colorability, and further provides a thermoplastic resin composition that has a good balance between surface appearance and impact resistance. Play.

  Hereinafter, the thermoplastic resin composition of the present invention will be described in detail.

  The butadiene rubber polymer forming the inner layer of the two-layer structure rubber polymer constituting the graft polymer (a-1) in the present invention is a diene monomer represented by, for example, 1,3-butadiene. A polymer obtained by polymerizing a monomer containing 50% by weight or more, and other monomers copolymerizable with the diene monomer include aromatic vinyl monomers such as styrene, acrylonitrile, etc. And an unsaturated carboxylic acid alkyl ester monomer such as methyl acrylate, ethyl acrylate and methyl methacrylate. Specific examples include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and butadiene-methyl methacrylate copolymer.

As the butadiene-based rubber polymer, it is necessary to use a butadiene-based rubber polymer having a weight average particle diameter of 250 nm to 400 nm. When the weight average particle diameter is less than 250 nm, the impact resistance and the thermal stability are inferior, and when it exceeds 400 nm, the gloss and blackness when colored in black are inferior. Further, as the butadiene-based rubber polymer, a rubber polymer having a predetermined weight average particle diameter (hereinafter referred to as unagglomerated and enlarged rubber) can be used. It is preferable to use an agglomerated rubber obtained by agglomerating rubber. Specifically, a butadiene rubber polymer latex obtained by agglomerating a butadiene rubber polymer latex having a weight average particle diameter of 50 nm to 200 nm and having a small particle diameter of 250 nm to 400 nm to be used is used. Is preferable from the viewpoint of bronze appearance.
As a method for agglomerating and enlarging the above-mentioned small particle size butadiene-based rubber polymer latex, a conventionally known method, for example, a method of adding an acidic substance (JP-B 42-3112, JP-B 55-19246, JP-B-2-9601). JP-A-63-117005, JP-A-63-132903, JP-A-7-157501, JP-A-8-259777), a method of adding an acid group-containing latex (JP-A-56-166201, JP-A-59-93701). JP-A-1-126301, JP-A-8-59704) and the like can be employed, and the method is not particularly limited, but an acidic substance is added to a small particle rubber latex to lower the pH of the latex to less than 7. The butadiene rubber polymer rubber is stabilized by adding a basic substance and stabilizing the pH higher than 7 after agglomeration and enlargement to a predetermined weight average particle diameter. It is preferred over the surface of the balance between impact resistance and gloss using the box.

The emulsifier used in the production of the above butadiene rubber latex (small particle size butadiene rubber latex and unagglomerated and enlarged rubber latex) is composed of a weak acid strong base salt such as fatty acid soaps, and has an acidic pH of 7 or less. Surfactants that lose their emulsifying action in the region can be used. For example, sodium salt and / or potassium salt of one or more acids such as lauric acid, oleic acid, stearic acid, mixed fatty acid, disproportionated rosin acid and the like can be mentioned. Particularly preferable examples include potassium salt or sodium salt of oleic acid, and potassium salt or sodium salt of disproportionated rosin acid, but not limited thereto.
Further, the amount of the emulsifier is not limited at all. However, when the polymerization stability of the rubber latex or the coagulation enlargement process is performed, it is 1 per 100 parts by weight of the rubber latex solid content in view of the subsequent coagulation enlargement treatment efficiency. It is preferable that it is 0.0-5.0 weight part.

Furthermore, the butadiene rubber latex (small particle diameter butadiene rubber latex and unagglomerated and enlarged rubber latex) can be obtained by a known emulsion polymerization using the above-mentioned surfactant as an emulsifier. Ordinary initiators, molecular weight regulators, polymerization aids such as electrolytes can be used.
Examples of the initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, and redox systems in which organic peroxides such as t-butylhydroxyperoxide and cumenehydroxyperoxide are combined with a reducing agent component. Examples of molecular weight modifiers include mercaptans (t-dodecyl mercaptan, n-dodecyl mercaptan, etc.), terpinolene, α-methylstyrene dimer, and the like. Further, examples of the electrolyte include basic substances such as sodium hydroxide, potassium hydroxide, and ammonium hydroxide, sodium chloride, potassium sulfate, sodium acetate, sodium sulfate, potassium phosphate, and 4 potassium pyrophosphate. Mixed use of more than one species is possible. Furthermore, although there is no restriction | limiting also about polymerization temperature, the range of 50-80 degreeC is preferable. The butadiene rubber latex (small particle size butadiene rubber latex and unagglomerated and enlarged rubber latex) can be obtained by the above emulsion polymerization, but as another method, a separately polymerized solid rubber-like heavy polymer can be obtained. It is also possible to obtain the coalescence by using, for example, a homogenizer and emulsifying with the above surfactant.

The above-mentioned small particle size butadiene rubber latex can be agglomerated and enlarged by contacting with an acidic substance. Examples of the acidic substance include mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, sodium hydrogen sulfate, Acidic salts such as sodium dihydrogen phosphate, organic acids such as oxalic acid, citric acid, acetic acid, formic acid, and acid anhydrides such as acetic anhydride can be used, and a mixture of two or more of these can also be used. Phosphoric acid, sulfuric acid, acetic anhydride and acetic acid are preferred. The amount of the acidic substance used may be any amount necessary to make the rubber latex acidic (pH 7 or lower), but the particle size of the rubber latex to be enlarged, the type and amount of the emulsifier, and the target enlarged rubber. It is appropriately adjusted depending on the particle size of the latex. The acidic substance is basically diluted with deionized water and added as an aqueous solution. The concentration of the acidic substance is not particularly limited. In order to prevent generation of substances and adhesion to the apparatus, the content is preferably from 0.3 to 10% by weight, and particularly preferably from 0.5 to 5.0% by weight.
Moreover, before adding an acidic substance, you may add the surfactant which has an acidic and favorable surface active ability previously to a small particle diameter butadiene-type rubber latex as needed. By adding a surfactant that is acidic and has a good surface-active ability in advance, it becomes easy to control the particle size of the latex at the time of agglomeration and enlargement.
Examples of such an acidic surfactant having good surface activity include sodium alkylbenzenesulfonate, sodium alkylnaphthalenesulfonate, potassium alkyldiphenylethersulfonate, and sodium lauryl sulfate. The amount of addition is not particularly limited, but can be appropriately adjusted depending on the concentration of acidic substance used for agglomeration enlargement, the type of small particle diameter butadiene rubber latex, the solid content concentration, and the like. A preferred addition amount is 0.3 parts by weight or less per 100 parts by weight of a small particle size butadiene rubber latex (solid content). Further, after the agglomeration and enlargement, a basic substance is added to the rubber latex, and the pH of the rubber latex is set to 7 or more, preferably 8 to 11. It is preferable in terms of preventing the occurrence of As said basic substance, sodium hydroxide, potassium hydroxide, etc. are mentioned, These can be used 1 type, or 2 or more types. In addition, the basic substance is basically diluted with deionized water and added as an aqueous solution, and there is no particular limitation on the concentration thereof. In order to prevent generation of coagulum and adhesion to the apparatus, the content is preferably 0.5 to 20% by weight, and particularly preferably 5 to 15% by weight.

The two-layer structure rubber polymer constituting the graft polymer (a-1) in the present invention comprises a butadiene-based rubber polymer having a weight average particle diameter of 250 nm to 400 nm and an alkyl in the presence or absence of a crosslinking agent. Acrylic acid ester monomer having 1 to 16 carbon atoms, for example, one or more of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., and other copolymers as required A two-layer rubber weight in which an inner layer formed by polymerizing one or more of possible monomers such as styrene, acrylonitrile, methyl methacrylate and the like is a butadiene rubber polymer and an outer layer is an acrylic rubber polymer. It is a coalescence. Here, as a usable crosslinking agent, for example, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl phthalate, dicyclopentadiene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Examples include pentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, and the like. Such a two-layer structure rubber polymer can be usually polymerized by emulsion polymerization, in which case a known emulsifier, for example, an anion such as sodium dodecylbenzenesulfonate, sodium oleate, dipotassium alkenyl succinate, etc. Nonionic emulsifiers such as polyemulsifier and polyoxyethylene nonylphenyl ether can be used. As the polymerization initiator, water-soluble and oil-soluble initiators alone or redox-based, for example, inorganic initiators such as persulfate, organic peroxides such as t-butyl hydroperoxide, azo compounds, etc. It can be used alone or in combination with sulfite, sodium formaldehyde sulfoxylate and the like as a redox initiator. Furthermore, if necessary, a polymerization chain transfer agent such as t-dodecyl mercaptan can be used.
The two-layer rubber polymer thus obtained is a butadiene rubber polymer having an inner layer having a weight average particle diameter of 250 nm to 400 nm and an outer layer having an average thickness of 70 nm to 180 nm. It is a two-layer rubber polymer which is a polymer.
The weight average particle size of the butadiene rubber polymer of the inner layer is not preferable because the impact resistance is poor when the weight average particle size is less than 250 nm, and the gloss is poor when the weight average particle size exceeds 400 nm.
The average thickness of the acrylic rubber polymer in the outer layer is not preferable because the impact resistance and the weather resistance are inferior when the average thickness of the outer layer is less than 70 nm, and the pigment colorability is inferior when it exceeds 180 nm.
In addition, as a method for controlling the average thickness of the acrylic rubber polymer of the outer layer, for example, when polymerizing the acrylic rubber polymer, the ratio of the butadiene rubber and the acrylate monomer and the amount of the emulsifier used Control. Increasing the ratio of acrylate monomer to butadiene rubber polymer and reducing the amount of emulsifier used increases the average thickness of the acrylic rubber polymer in the outer layer. When the ratio of the acid ester monomer is decreased and the amount of the emulsifier used is increased, the average thickness of the acrylic rubber polymer in the outer layer is reduced.

The acrylic rubber polymer constituting the graft polymer (a-2) in the present invention is an acrylic acid ester monomer having 1 to 16 carbon atoms in the alkyl group in the presence or absence of a crosslinking agent, For example, one or more of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like, and another copolymerizable monomer as necessary, for example, styrene, acrylonitrile, methyl methacrylate, etc. Or it is a rubber polymer which polymerizes 2 or more types. Here, as a usable crosslinking agent, for example, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl phthalate, dicyclopentadiene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Examples include pentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, and the like. Such an acrylate rubber polymer can be usually polymerized by emulsion polymerization, in which case a known emulsifier such as sodium dodecylbenzenesulfonate, sodium oleate, dipotassium alkenyl succinate, etc. Nonionic emulsifiers such as anionic emulsifiers and polyoxyethylene nonylphenyl ether can be used. As the polymerization initiator, water-soluble and oil-soluble initiators alone or redox-based, for example, inorganic initiators such as persulfate, organic peroxides such as t-butyl hydroperoxide, azo compounds, etc. It can be used alone or in combination with sulfite, sodium formaldehyde sulfoxylate and the like as a redox initiator. Furthermore, if necessary, a polymerization chain transfer agent such as t-dodecyl mercaptan can be used.
The acrylic rubber polymer has a weight average particle diameter of 70 nm to 180 nm. When the weight average particle diameter is less than 70 nm, the impact resistance and thermal stability are inferior, and when it exceeds 180 nm, the pigment colorability is inferior.
The acrylic rubber polymer constituting the graft polymer (a-2) can be produced by the above-described polymerization. When the two-layer rubber polymer described in [0012] is polymerized, It is also possible to polymerize with a structural rubber polymer. Specifically, when the two-layer structure rubber polymer is polymerized, the acrylate monomer is added in two stages, and the acrylate monomer is added in the second stage. An acrylic rubber polymer having a desired weight average particle diameter can be polymerized by adding it together with an emulsifier to form new particles.

Examples of the aromatic vinyl monomer constituting the graft polymer (A) [(a-1) and (a-2)] in the present invention include styrene, α-methylstyrene, p-methylstyrene, and t-butyl. Styrene, dimethyl styrene, etc. are mentioned, 1 type, or 2 or more types can be used. Of these, styrene is particularly preferred. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and one or more of them can be used. Of these, acrylonitrile is particularly preferred. Further, in the present invention, other aromatic vinyl monomers that can be copolymerized with the above aromatic vinyl monomer and vinyl cyanide monomer within a range not hindering the effect thereof, for example, (meth) acrylic acid esters. Monomer (methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.)), unsaturated carboxylic acid or anhydride thereof (acrylic acid, methacrylic acid, maleic acid) Anhydrides, etc.), maleimide monomers (maleimide, methylmaleimide, ethylmaleimide, N-phenylmaleimide, etc.), amide monomers (acrylamide, methacrylamide, etc.), etc. be able to.
The composition ratio of each component constituting the graft polymer (A) [(a-1) and (a-2)] is not particularly limited, but preferably 5 to 70% by weight of a rubbery polymer and It is 30 to 95% by weight of a monomer mainly composed of an aromatic vinyl monomer and a vinyl cyanide monomer.
The graft ratio of the graft polymer (A) [(a-1) and (a-2)] is not particularly limited, but is 20 to 100% in view of balance of physical properties such as impact resistance. It is preferable.
There is no restriction | limiting in the polymerization method of graft polymer (A) [(a-1) and (a-2)] in this invention, well-known emulsion polymerization method, block polymerization method, solution polymerization method, suspension polymerization method, or these Although any combination of these polymerization methods can be employed, emulsion polymerization is particularly preferred.
Regarding the graft polymer (a-1) and graft polymer (a-2) constituting the graft polymer (A), an aromatic vinyl monomer and cyanide in the presence of each rubber polymer. The graft polymer (A) can be used by graft polymerization of a monomer mainly composed of a vinyl monomer and then mixed at a predetermined ratio. Grafting of monomers composed mainly of aromatic vinyl monomers and vinyl cyanide monomers in the presence of mixed rubber polymers in which structural rubber polymers and acrylic rubber polymers are mixed at a specified ratio It is also possible to use a graft polymer obtained by polymerization as the graft polymer (A).

The proportion of the graft polymer (a-1) and the graft polymer (a-2) used in the graft polymer (A) of the present invention is 1 to 40% by weight of the graft polymer (a-1) and the graft polymer ( a-2) 60 to 99% by weight, preferably 3 to 15% by weight of the graft polymer (a-1) and 85 to 97% by weight of the graft polymer (a-2).
When the graft polymer (a-1) is less than 1% by weight (the graft polymer (a-2) exceeds 99% by weight), the impact resistance is poor, and 40% by weight (the graft polymer (a-2) is 60%). If it exceeds less than% by weight, the gloss and weather resistance are inferior, which is not preferred.

The thermoplastic resin (B) in the present invention is at least one selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers, and other vinyl monomers. It is a thermoplastic resin (B) obtained by polymerizing monomers.
Examples of the aromatic vinyl monomer constituting the thermoplastic resin (B) include styrene, α-methylstyrene, vinyltoluene and the like, and styrene is particularly preferable. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. Furthermore, examples of the (meth) acrylic acid ester monomer include methyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the like. In particular, methyl methacrylate is preferred.
In the present invention, other vinyls that can be copolymerized with the above aromatic vinyl monomer, vinyl cyanide monomer and (meth) acrylate monomer within the range not impeding the effect. It is also possible to use a system monomer. Examples of such other vinyl monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride or anhydrides thereof, and maleimides such as maleimide, methylmaleimide, ethylmaleimide, and N-phenylmaleimide. Examples include monomers, amide monomers such as acrylamide and methacrylamide, and the like, and one kind or two or more kinds can be used. Further, these other copolymerizable monomers can be used in the range of 0 to 40% by weight in the thermoplastic resin (B).
In addition, although there is no restriction | limiting in particular in the intrinsic viscosity (measured at 25 degreeC as a 0.2g / 100cc N, N dimethylformamide solution) of a thermoplastic resin (B), It is preferable that it is 0.2-1.2.

  There is no restriction | limiting in the polymerization method of the thermoplastic resin (B) in this invention, Adopting the method which combined the well-known emulsion polymerization method, block polymerization method, solution polymerization method, suspension polymerization method, or these polymerization methods arbitrarily. Can do.

  The thermoplastic resin composition in the present invention comprises 10 to 100 parts by weight of the above graft copolymer (A) and 0 to 90 parts by weight of the thermoplastic resin (B) (however, the sum of (A) and (B) is 100 parts by weight). If the graft polymer (A) component is less than 10% by weight, the impact resistance is inferior, which is not preferable.

  The thermoplastic resin composition of the present invention includes various additives as necessary, for example, known antioxidants, light stabilizers, lubricants, plasticizers, antistatic agents, colorants, flame retardants, matting agents, and fillers. An agent or the like can be appropriately added. In mixing, a known kneading apparatus such as an extruder, a roll, a Banbury mixer, or a kneader can be used.

The thermoplastic resin composition thus obtained can of course be used alone, but can also be used by mixing with other thermoplastic resins as necessary.
Examples of such other thermoplastic resins include polycarbonate resin, polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-acrylonitrile-methyl methacrylate copolymer, polymethyl methacrylate, Styrene-maleic anhydride copolymer, styrene-maleimide copolymer, acrylonitrile-styrene-maleimide copolymer, rubber reinforced polystyrene resin (HIPS resin), acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-ethylene propylene -Styrene resin (AES resin), methyl methacrylate-butadiene-styrene resin (MBS resin), and the like.

  Furthermore, the thermoplastic resin composition of the present invention can be molded as various molded parts by known molding methods such as injection molding, blow molding, press molding, and the like.

  Prior to the description of the examples, the weight average particle diameter measurement method of the inner layer butadiene rubber polymer of the graft polymer (a-1) defined in this patent, the average thickness measurement method of the outer layer acrylic rubber polymer, the graft A method for measuring the weight average particle diameter of the acrylic rubber polymer of the polymer (a-2) and a method for measuring the weight ratio of the graft polymer (a-1) and the graft polymer (a-2) are described.

[Method of measuring weight average particle diameter of butadiene rubber polymer and average thickness of acrylic rubber polymer of graft polymer (a-1)]
An ultrathin section is cut out at −60 ° C. using a cryomicrotome from a molded piece of the resin composition molded in accordance with ISO test method 294. Then, after dyeing with the obtained osmium tetroxide (OsO4), it was further dyed with ruthenium tetroxide (RuO4), and the dispersed particles of the graft polymer were observed and photographed using a transmission electron microscope.
Osmium tetroxide dyes butadiene rubber polymer, and ruthenium tetroxide separates butadiene rubber polymer, acrylic rubber polymer and graft polymer layer, allowing observation of two-layer rubber polymer It becomes.
The weight average particle diameter of the butadiene rubber polymer and the average thickness of the acrylic rubber polymer were measured by the following procedure using an image analysis process (device name: IP-1000PC manufactured by Asahi Kasei Corporation). For each rubber particle, the equivalent circle diameter (radius) is obtained from the measurement of the area including the surface acrylic rubber polymer layer, and the same applies to the butadiene rubber polymer excluding the surface acrylic rubber polymer layer. The equivalent circle diameter (radius) was determined, and the weight average particle diameter of the butadiene rubber polymer and the average thickness of the acrylic rubber polymer were calculated. In this invention, it is the average value measured about 15 or more of two-layer structure rubber polymer particles.

[Method for measuring weight average particle diameter of acrylic rubber polymer of graft polymer (a-2)]
An ultrathin section is cut out at −60 ° C. using a cryomicrotome from a molded piece of the resin composition molded in accordance with ISO test method 294. Then, after dyeing with the obtained osmium tetroxide (OsO4), it was further dyed with ruthenium tetroxide (RuO4), and the dispersed particles of the graft polymer were observed and photographed using a transmission electron microscope.
Osmium tetroxide dyes butadiene rubber polymer, and ruthenium tetroxide separates butadiene rubber polymer, acrylic rubber polymer, and graft polymer layer. The rubber polymer can be identified.
The weight average particle diameter of the acrylic rubber polymer was measured using an image analysis process (apparatus name: IP-1000PC manufactured by Asahi Kasei Co., Ltd.) according to the following procedure. The area of each rubber particle was measured, its equivalent circle diameter (radius) was determined, and the weight average particle diameter of the acrylic rubber polymer was calculated.

[Measurement method of weight ratio of graft polymer (a-1) and graft polymer (a-2)]
An ultrathin section is cut out at −60 ° C. using a cryomicrotome from a molded piece of the resin composition molded in accordance with ISO test method 294. Then, after dyeing with the obtained osmium tetroxide (OsO4), it was further dyed with ruthenium tetroxide (RuO4), and the dispersed particles of the graft polymer were observed and photographed using a transmission electron microscope.
Osmium tetroxide dyes butadiene rubber polymer, and ruthenium tetroxide separates butadiene rubber polymer, acrylic rubber polymer, and graft polymer layer. The rubber polymer can be identified.
The area of each two-layer rubber polymer and acrylic rubber polymer was measured, and the weight ratio was calculated.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part and% which are shown in an Example are based on a weight.

[Reference Example-1] Production of butadiene rubber polymer latex (I) After replacing the inside of a 10 liter pressure vessel with nitrogen, 100 parts by weight of 1,3-butadiene, 0.5 parts by weight of n-dodecyl mercaptan, excess 0.3 part by weight of potassium sulfate, 0.8 part by weight of disproportionated sodium rosinate, 0.1 part by weight of sodium hydroxide and 130 parts by weight of deionized water were charged and reacted at 70 ° C. for 20 hours while stirring. Thereafter, 0.6 parts by weight of disproportionated sodium rosinate, 0.1 parts by weight of sodium hydroxide and 5 parts by weight of deionized water were added. Further, after 10 hours while maintaining the temperature at 70 ° C., 0.6 parts by weight of disproportionated sodium rosinate, 0.1 parts by weight of sodium hydroxide and 5 parts by weight of deionized water were added and stirring was continued for 5 hours. The reaction was terminated. Thereafter, the remaining 1,3-butadiene was removed under reduced pressure to obtain a butadiene-based rubber polymer latex (I).
The obtained butadiene-based rubber polymer latex (I) was stained with osmium tetroxide (OsO4), dried, and photographed with a transmission electron microscope. The area of each rubber particle is measured using an image analysis process (apparatus name: IP-1000PC manufactured by Asahi Kasei Co., Ltd.), the equivalent circle diameter (radius) is obtained, and the weight of the butadiene rubber polymer latex (I) As a result of calculating the average particle size, the weight average particle size was 330 nm.

[Reference Example-2]
After replacing the inside of the 10 liter pressure vessel with nitrogen, 1,3-butadiene 100 parts by weight, n-dodecyl mercaptan 0.5 parts by weight, potassium persulfate 0.3 parts by weight, disproportionated sodium rosinate 1.8 Part by weight, 0.1 part by weight of sodium hydroxide, and 145 parts by weight of deionized water were added and reacted at 70 ° C. for 8 hours with stirring. Thereafter, 0.2 parts by weight of disproportionated sodium rosinate, 0.1 parts by weight of sodium hydroxide and 5 parts by weight of deionized water were added. Further, stirring was continued for 6 hours while maintaining the temperature at 70 ° C. to complete the reaction. Thereafter, the remaining 1,3-butadiene was removed under reduced pressure to obtain a butadiene-based rubber polymer latex (II).
As a result of calculating the weight average particle diameter of the butadiene-based rubber polymer latex (II) by the same method as in Reference Example-1, the weight average particle diameter was 120 nm.

[Reference Example-3]
To a 10 liter pressure vessel, 270 parts by weight of the butadiene rubber latex (II) obtained in Reference Example-2 and 0.1 part by weight of sodium dodecylbenzenesulfonate were added and mixed with stirring for 10 minutes. 20 parts by weight of an aqueous acid solution was added over 10 minutes. Next, 10 parts by weight of a 10% aqueous potassium hydroxide solution was added to obtain an agglomerated butadiene rubber latex (III).
As a result of calculating the weight average particle diameter of the butadiene-based rubber polymer latex (III) by the same method as in Reference Example-1, the weight average particle diameter was 330 nm.

[Reference Example-4]
After adding 270 parts by weight of the butadiene rubber latex (II) obtained in Reference Example-2 and 0.03 part by weight of sodium dodecylbenzenesulfonate to a 10 liter pressure vessel, the mixture was stirred for 10 minutes and mixed with 5% phosphorus. 20 parts by weight of an aqueous acid solution was added over 30 minutes. Next, 10 parts by weight of a 10% aqueous potassium hydroxide solution was added to obtain an agglomerated butadiene rubber latex (IV).
As a result of calculating the weight average particle diameter of the butadiene-based rubber polymer latex (IV) by the same method as in Reference Example-1, the weight average particle diameter was 460 nm.

[Production of (Acrylate ester-based rubber polymer latex- (1) to (4))]
In a nitrogen-replaced glass reactor, 200 parts by weight of deionized water, 5 parts by weight of butadiene rubber polymer latex (I) in terms of solid content, 5 parts by weight of butyl acrylate, 0.05 parts by weight of allyl methacrylate, oleic acid 0.15 parts by weight of potassium and 0.3 parts by weight of potassium persulfate were added and reacted at 65 ° C. for 1 hour with stirring. Then, an emulsifier aqueous solution in which 1.0 part by weight of potassium oleate was dissolved in 90 parts by weight of butyl acrylate and 0.90 part by weight of allyl methacrylate and 20 parts by weight of deionized water was continuously added over 4 hours. Then, superposition | polymerization was continued at 65 degreeC for 3 hours, superposition | polymerization was complete | finished, and acrylic acid ester system rubber polymer latex- (1) was obtained.
Moreover, except having changed the butadiene type rubber polymer latex as shown in Table 1, it manufactured similarly and obtained acrylic acid ester type rubber polymer latex-(2)-(4).

In a nitrogen-replaced glass reactor, 200 parts by weight of deionized water, 5 parts by weight of butadiene rubber polymer latex (III), 15 parts by weight of butyl acrylate, 0.15 parts by weight of allyl methacrylate, persulfate 0.3 parts by weight of potassium was charged and reacted at 65 ° C. for 1.5 hours with stirring. Thereafter, an emulsifier aqueous solution in which 1.2 parts by weight of potassium oleate was dissolved in 80 parts by weight of butyl acrylate and 0.80 part by weight of allyl methacrylate and 20 parts by weight of deionized water was continuously added over 3.5 hours. . Thereafter, the polymerization was continued at 65 ° C. for 3 hours to complete the polymerization, and the acrylic ester rubber polymer latex- (5)

In a nitrogen-replaced glass reactor, 200 parts by weight of deionized water, 5 parts by weight of butadiene rubber polymer latex (III) in terms of solid content, 0.25 parts by weight of potassium oleate, and 0.3 parts by weight of potassium persulfate were added. The temperature was raised to 65 ° C. while charging and stirring. Thereafter, a mixed solution of 95 parts by weight of butyl acrylate and 0.95 part by weight of allyl methacrylate and an aqueous emulsifier solution in which 0.9 part by weight of potassium oleate was dissolved in 20 parts by weight of deionized water were continuously added over 4.5 hours. . Thereafter, the polymerization was continued at 65 ° C. for 3 hours to complete the polymerization, and the acrylic ester rubber polymer latex- (6)

In a nitrogen-replaced glass reactor, 200 parts by weight of deionized water, 5 parts by weight of butadiene rubber polymer latex (III) in terms of solid content, 5 parts by weight of butyl acrylate, 0.05 parts by weight of allyl methacrylate, oleic acid 0.15 parts by weight of potassium and 0.3 parts by weight of potassium persulfate were added and reacted at 65 ° C. for 1 hour with stirring. Thereafter, a mixed solution of 90 parts by weight of butyl acrylate and 0.90 part by weight of allyl methacrylate and an aqueous emulsifier solution in which 0.50 part by weight of potassium oleate was dissolved in 20 parts by weight of deionized water were continuously added over 4 hours. Then, superposition | polymerization was continued at 65 degreeC for 3 hours, superposition | polymerization was complete | finished, and acrylic acid ester system rubber polymer latex- (7) was obtained.

In a nitrogen-replaced glass reactor, 200 parts by weight of deionized water, 5 parts by weight of butadiene rubber polymer latex (III) in terms of solid content, 5 parts by weight of butyl acrylate, 0.05 parts by weight of allyl methacrylate, oleic acid 0.15 parts by weight of potassium and 0.3 parts by weight of potassium persulfate were added and reacted at 65 ° C. for 1 hour with stirring. Thereafter, an aqueous emulsifier solution in which 3.0 parts by weight of potassium oleate was dissolved in 90 parts by weight of butyl acrylate and 0.90 parts by weight of allyl methacrylate and 20 parts by weight of deionized water was continuously added over 4 hours. Then, superposition | polymerization was continued at 65 degreeC for 3 hours, superposition | polymerization was complete | finished, and acrylic acid ester system rubber polymer latex- (8) was obtained.

In a nitrogen-replaced glass reactor, 200 parts by weight of deionized water, 50 parts by weight of butadiene rubber polymer latex (III) in terms of solid content, 25 parts by weight of butyl acrylate, 0.25 parts by weight of allyl methacrylate, potassium persulfate 0.3 part by weight was charged and reacted at 65 ° C. for 2 hours with stirring. Thereafter, an emulsifier aqueous solution in which 0.50 part by weight of potassium oleate was dissolved in 25 parts by weight of butyl acrylate and 0.25 part by weight of allyl methacrylate and 20 parts of deionized water was continuously added over 2.5 hours. . Thereafter, the polymerization was continued at 65 ° C. for 2 hours, the polymerization was terminated, and an acrylate rubber polymer latex- (9) was obtained.

A nitrogen-replaced glass reactor was charged with 200 parts by weight of deionized water, 10 parts by weight of butyl acrylate, 0.10 parts by weight of allyl methacrylate, 0.15 parts by weight of potassium oleate, and 0.3 parts by weight of potassium persulfate. The mixture was reacted at 65 ° C. for 1 hour with stirring. Thereafter, an aqueous emulsifier solution in which 1.50 parts by weight of potassium oleate was dissolved in 90 parts by weight of butyl acrylate and 0.90 parts by weight of allyl methacrylate and 20 parts by weight of deionized water was continuously added over 4 hours. Then, superposition | polymerization was continued at 65 degreeC for 3 hours, superposition | polymerization was complete | finished, and acrylic acid ester system rubber polymer latex- (10) was obtained.

[Production of Graft Polymer (A-1 to 10)]
Into a nitrogen-replaced glass reactor, 50 parts by weight of acrylate rubber polymer latex (1), 130 parts by weight of deionized water, 0.1 part by weight of dextrin, 0.1 part by weight of anhydrous sodium pyrophosphate And an aqueous solution in which 0.005 part by weight of ferrous sulfate was dissolved, and the temperature was raised to 70 ° C. Thereafter, an emulsifier aqueous solution in which 1.0 part by weight of potassium oleate was dissolved in 15 parts by weight of acrylonitrile, 35 parts by weight of styrene and 0.3 part by weight of cumene hydroperoxide and 20 parts by weight of deionized water was added over 4 hours. Added continuously. Thereafter, the polymerization was continued for 3 hours to complete the polymerization. Thereafter, salting out, dehydration and drying were performed to obtain a graft polymer (A-1).
Moreover, it manufactured similarly except having changed acrylic acid ester system rubber polymer latex as shown in Table 1, and obtained graft polymer A-2-8.

Copolymer (B)
SAN resin (manufactured by Nippon A & L Co., Ltd., Litec-A 230 PCU)

[Examples 1 to 3, Comparative Examples 1 to 8]
After the graft polymer (A) and the copolymer (B) were mixed at the composition ratio shown in Table 2, the mixture was melt-kneaded at 240 ° C. using a 40 mm twin screw extruder to be pelletized. Various test pieces were formed from the obtained pellets in accordance with ISO test method 294 to produce various test pieces, and the physical properties were measured. In addition, each evaluation method is shown below.

(1) Impact resistance: Based on ISO 179, a Charpy impact value with a notch was measured at a thickness of 4 mm. Unit: kJ / m ²
(2) Fluidity: Melt volume flow rate was measured according to ISO1133. Unit; cm ^3/10 minutes

1.0 part of carbon # 45B (Mitsubishi Chemical Corporation) is mixed with 100 parts by weight of the graft copolymer (A) and copolymer (B) having the composition ratio shown in Table 2, and 40 mm biaxial. It was melt-kneaded at 250 ° C. using an extruder to obtain colored pellets. A molded product (150 mm × 120 mm × 3 mm) was molded from the obtained colored pellets with an injection molding machine set at 250 ° C.
(3) Gloss: Surface gloss was measured according to ASTM D-523. unit;%
(4) Jetness: evaluated by hue measurement according to JIS Z8729.
(5) Bronze phenomenon: The bronze phenomenon was judged visually at noon outdoors and in direct sunlight. Bronze phenomenon was absent, Bronze phenomenon was slightly present, and bronze phenomenon was marked.

(6) Thermal stability: After mixing the graft polymer (A) and copolymer (B) at the composition ratio shown in Table 2, the mixture is melt-kneaded at 240 ° C. using a 40 mm twin screw extruder and pellets. Turned into. A 150 mm × 120 mm × 3 mm flat plate was molded with an injection molding machine, and the occurrence of a rubber leak on the surface of the molded product was visually determined. The set temperature of the molding machine cylinder was 280 ° C., the molding cycle was 60 seconds / 1 shot, and the 20th shot sample was visually confirmed. No occurrence of rubber burst leak.

As described above, according to the present invention, a thermoplastic resin composition that solves the bronze phenomenon and has excellent weather resistance and pigment colorability. Furthermore, there is an effect that a thermoplastic resin composition having a good balance between surface appearance and impact resistance can be obtained, interior and exterior parts for vehicles such as automobiles, housings for various home appliances and OA equipment, and other miscellaneous goods fields. Etc., and can be suitably used in a wide range of fields.

Claims (3)

To the two-layer rubber polymer in which the inner layer is a butadiene rubber polymer having a weight average particle diameter of 250 nm to 400 nm and the outer layer is an acrylic rubber polymer having an average thickness of 70 nm to 180 nm, 1 to 40% by weight of a graft polymer (a-1) obtained by graft polymerization of a monomer and a monomer mainly composed of vinyl cyanide monomer,
A graft polymer obtained by graft polymerization of an acrylic rubber polymer having a weight average particle diameter of 70 nm to 180 nm with an aromatic vinyl monomer and a monomer mainly composed of vinyl cyanide monomer (a- 2) 10 to 100 parts by weight of the graft copolymer (A) comprising 60 to 99% by weight, an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth) acrylate monomer and other vinyls It consists of 0 to 90 parts by weight of a thermoplastic resin (B) obtained by polymerizing at least one monomer selected from the group consisting of monomers (however, the sum of (A) and (B) is 100 parts by weight). Thermoplastic resin composition.   The butadiene rubber polymer is a butadiene rubber polymer latex in which a small particle size butadiene rubber polymer latex having a weight average particle size of 50 nm to 200 nm is agglomerated and enlarged to a weight average particle size of 250 nm to 400 nm. The thermoplastic resin composition according to claim 1.   Butadiene rubber polymer is an acidic substance added to a small particle diameter butadiene rubber polymer latex having a weight average particle diameter of 50 nm to 200 nm, and the latex has a pH lower than 7 to make the latex particles have a weight average particle diameter of 250 nm or more. The thermoplastic resin composition according to claim 1, wherein a butadiene-based rubber polymer latex is used which is stabilized by increasing the pH of the latex to be higher than 7 by adding a basic substance and then aggregating and enlarging to ˜400 nm or less. .